WO2007094213A1 - dispositif d'impression et procédé d'impressioN - Google Patents

dispositif d'impression et procédé d'impressioN Download PDF

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Publication number
WO2007094213A1
WO2007094213A1 PCT/JP2007/052115 JP2007052115W WO2007094213A1 WO 2007094213 A1 WO2007094213 A1 WO 2007094213A1 JP 2007052115 W JP2007052115 W JP 2007052115W WO 2007094213 A1 WO2007094213 A1 WO 2007094213A1
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WO
WIPO (PCT)
Prior art keywords
transfer
pressure
imprint apparatus
transfer material
mold
Prior art date
Application number
PCT/JP2007/052115
Other languages
English (en)
Japanese (ja)
Inventor
Yasuo Hosoda
Tetsuya Imai
Original Assignee
Pioneer Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pioneer Corporation filed Critical Pioneer Corporation
Priority to US12/279,481 priority Critical patent/US7857611B2/en
Priority to JP2008500457A priority patent/JPWO2007094213A1/ja
Publication of WO2007094213A1 publication Critical patent/WO2007094213A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023Microembossing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00Shaping characteristics in general
    • B29C2791/004Shaping under special conditions
    • B29C2791/006Using vacuum
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/855Coating only part of a support with a magnetic layer

Definitions

  • the present invention relates to an imprint apparatus and imprint method for forming a transferred product by pressing a transfer mold having a concavo-convex pattern against a transfer material to transfer the concavo-convex corresponding to the concavo-convex pattern.
  • Patent Document 1 discloses a method for manufacturing a sheet for an information recording medium in which a hydrogen styrene-based polymer sheet is brought into contact with a stamper under a reduced pressure of 30 kPa or less and heated and pressed.
  • Patent Document 2 discloses an optical recording substrate that is heated and pressed by bringing an organic polymer sheet having a roughened surface into contact with a stamper under reduced pressure.
  • Patent Document 3 discloses that a stamper groove is formed on a sheet having a thickness of 0.2 mm or less, a vacuum of 13.33 Pa or less, a temperature of 150 to 300 ° C, a pressure of 0.5 to: LOkgZcm 2.
  • An apparatus for transferring a shape to form a cover layer of an optical information recording medium is disclosed.
  • Patent Document 4 manufactures a recording medium that does not generate bubbles on the surface of a plate-like or sheet-like substrate or recording layer, and presses and transfers a stamper surface pattern in a reduced pressure environment or in a vacuum. Is disclosed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-173584 (paragraph numbers 0048 to 0068)
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-109254 (paragraph numbers 0010 to 0042)
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-67989 (paragraph numbers 0011 to 0056)
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-42387 (paragraph numbers 0025 to 0068)
  • transfer is performed by pressing the transfer mold against the transfer material.
  • the transfer material enters the recess pattern of the transfer mold by a compressive force, and enters the recess pattern.
  • Corresponding convex patterns are formed.
  • air may also enter the concave part. The air that has entered the recesses is sealed to the back of the recesses by the transfer material and there is no escape space, so the presence of this sealed air has a significant effect on the transfer performance.
  • Patent Document 1 The prior art described in Patent Document 1 mainly uses a 20-ton press to limit the atmospheric pressure under a specific pressing pressure condition so that air is not caught. Therefore, no consideration is given to enabling a desired transfer even if air is caught.
  • the pressing force pressing pressure
  • the pressing force is not specifically defined, and even if the pressing force changes, there is a possibility that sufficient transfer cannot be obtained even under the prescribed reduced pressure.
  • each of the above prior arts is an imprint apparatus as an advanced form of a resin molding apparatus or a press apparatus that determines conditions by paying attention to the relationship between temperature and pressure under normal pressure, or true
  • An imprinting device is used as a development of an ultraviolet curing resin transfer device that attempts imprinting in an air environment with almost no pressure.
  • the limited preferred operating conditions when using these imprinting devices are merely determined by trial and error, and even when air enters the transfer-type recess pattern together with the transfer material, the desired transfer can be performed. The conditions for doing so were not considered at all.
  • the problems to be solved by the present invention include the above-described problems as an example.
  • the invention according to claim 1 is characterized in that a transfer substrate on which a transfer material is placed, a transfer mold having a concave pattern, and the transfer mold at an effective pressure Mo [Pa].
  • An imprint apparatus comprising: a pressure adjusting unit for performing; and a control unit, wherein the imprint apparatus forms a transfer product having a convex pattern corresponding to the concave pattern.
  • the control means controls the pressing means and the pressure adjusting means based on the depth K [nm] of the concave pattern of the transfer mold and the height k [nm] of the convex pattern of the transferred material.
  • the invention according to claim 2 is the configuration of claim 1, characterized in that the pressure adjusting means is a pressure reducing means.
  • the invention according to claim 3 is the configuration according to claim 1 or claim 2, wherein the control means satisfies the pressing means so as to satisfy MoZP ⁇ kZ (K-k). And controlling the pressure adjusting means.
  • the invention according to claim 8 is the configuration according to claim 1 or claim 2, wherein the control means is configured such that the height k [nm] of the convex pattern is greater than the depth K.
  • the pressing means and the pressure adjusting means are controlled to satisfy 1. lkZ (K— 1. Ik) ⁇ Mo / P ⁇ 0.9k / (K-0.9k) And
  • the invention according to claim 10 is characterized in that a transfer mold having a concave pattern of depth K [nm] is provided with fluidity in an atmospheric pressure P [Pa]. After pressing against the transfer material with an effective pressure Mo [Pa], and curing the transfer material in the pressed state, the height corresponding to the recess pattern is removed by peeling off the transfer mold.
  • the pressing and the atmospheric pressure are set so that MoZP ⁇ kZ (K ⁇ k).
  • the invention according to claim 11 is characterized in that a transfer mold having a concave pattern of depth K [nm] is provided with fluidity in an atmospheric pressure P [Pa]. After pressing against the transfer material with an effective pressure Mo [Pa], and curing the transfer material in the pressed state, the height corresponding to the recess pattern is removed by peeling off the transfer mold.
  • an imprint that uses an ultraviolet-curing resin or the like that has a small temperature change during imprinting is used as a transfer material.
  • 1 is an embodiment of a remote device.
  • FIG. 1 is a conceptual configuration diagram showing an overall schematic structure of an imprint apparatus 100 according to the present embodiment.
  • an imprint apparatus 100 includes a vacuum chamber 1 constituting a decompression chamber 1 and a transfer material 2 provided in the vacuum chamber 1 and having fluidity under predetermined conditions (in this example, the temperature during imprinting).
  • the mold holding mechanism 5 for supporting the mold 4 against the wall surface of the vacuum chamber 1 (the upper wall in this example) and the vacuum chamber 1 are connected to the vacuum chamber 1 through the optical fiber 6, and ultraviolet rays are injected into the vacuum chamber 1.
  • An ultraviolet lamp 7 for supply, an ultraviolet irradiation lens 8 for expanding the ultraviolet beam introduced into the vacuum chamber 1, and an upper portion of the transfer mold 4 are provided to transfer the expanded ultraviolet beam.
  • Transfer material through mold 4 A transparent support window 9 for irradiating the material, a pressurizing mechanism 10 (pressing means) for generating a pressing force for pressing the transfer mold 4 against the transfer material 2 on the transfer substrate 3, and a vacuum chamber 1 It has a vacuum pump 13 (pressure reduction means) that is connected via a pipe line 12 equipped with a valve 11 and depressurizes the atmosphere in the vacuum chamber 11.
  • the pressurizing mechanism 10 can be moved up and down by being screwed to a drive shaft 14 rotated by a hydraulic actuator (not shown) and a screw provided on the surface of the drive shaft 14, for example.
  • the transfer substrate 3 is provided on the substrate support 15. Further, the pressurizing mechanism 10 presses the transfer mold 4 against the transfer material 2 at a pressure M [Pa] (in this case, equal to the effective pressure Mo. See also a modification of (1) described later).
  • the pressing force is set.
  • the pressing force may be fixedly set, may be variably set by an operator via an operating means (not shown), or may be automatically variably set.
  • the vacuum suction force of the vacuum pump 13 is set so that the transfer space R in the vacuum chamber 11 where the transfer mold 4 and the transfer substrate 3 are present is reduced to a pressure P [Pa].
  • the pump suction force may be fixed, or may be variably set by an operator via an operating means (not shown), or may be automatically variably set.
  • FIGS. 2 (a) to 2 (f) show the embodiment of the present invention implemented using the imprint apparatus 100 configured as described above. It is explanatory drawing which represents each procedure of the imprint method notionally.
  • a transfer material 2 (ultraviolet curable resin) is passed through a nozzle 16 (not shown in FIG. 1) provided in an appropriate manner in a vacuum chamber 11. ) To form a layer of transfer material 2 (FIG. 2 (b)).
  • the vacuum pump 13 is operated to reduce the atmospheric pressure of the transfer space R in the vacuum chamber 11 to P [Pa] (Fig. 2 (c)).
  • the pressure mechanism 10 is operated to raise the substrate support 15, thereby pressing the transfer mold 4 against the transfer material 2 on the transfer substrate 3 with the pressure M (FIG. 2). (d)). With the transfer mold 4 pressed, the ultraviolet lamp 7 is operated to irradiate the transfer material 2 with ultraviolet rays, thereby curing the transfer material 2 (FIG. 2 (e)).
  • the pressurizing mechanism 10 is operated again to lower the substrate support 15 and thereby the transfer mold 4 is peeled off from the transfer material 2, thereby supporting the concave pattern 4A.
  • a transfer material 17 having a convex pattern 17A having a corresponding height k [nm] is formed (FIG. 2 (f)).
  • the operation of the vacuum pump 13 is stopped, the atmospheric pressure of the transfer space R in the vacuum chamber 1 is returned to atmospheric pressure, and the transfer substrate 3 on which the formed transfer material 17 is placed is not illustrated.
  • the vacuum chamber 11 is taken out through the opening / closing means, and the transfer is completed.
  • the pressurizing mechanism 10 and the vacuum pump 13 are configured such that the concave pattern depth K of the transfer mold 4, the convex pattern height k of the transfer material, With regard to the pressure M when the transfer mold 4 is pressed and the pressure P in the transfer space R, the pressing force is generated and the pressure is reduced so that M / P ⁇ k Z (K ⁇ k) is satisfied. ing.
  • FIG. 3 is a flowchart conceptually showing each procedure of the imprint method performed using the imprint apparatus 100 having the above configuration. Note that the content of this flowchart shows an example of work performed by the control means in the imprint apparatus 100, and mainly represents, for example, a flow from the viewpoint of a control program. In this flowchart, for example, the UV method (ultraviolet irradiation method) is adopted.
  • the UV method ultraviolet irradiation method
  • step S1 the transfer mold 4 is set.
  • step S2 the control program instructs the transfer substrate 3 to be set.
  • a layer of the transfer material 2 (ultraviolet curing resin) is formed on the transfer substrate 3 by using a coating apparatus prepared separately in advance.
  • the nozzle 16 (not shown in FIG. 1) provided in an appropriate manner in the vacuum chamber 11 is further provided on the control program force transfer substrate 3 in this step S2.
  • the transfer material 2 is applied to form a layer of the transfer material 2.
  • step S3 parameters are set. Specifically, the depth K of the concave pattern 4A and the height k of the convex pattern 7A formed on the transfer material 2 are input.
  • the pressurizing mechanism 10 and the vacuum pump 13 are pressed against the depth K of the concave pattern 4A of the transfer mold 4, the height k of the convex pattern 7 of the transfer material 2, and the transfer mold 4 is pressed.
  • the pressing force is generated and the pressure is reduced so that M / P ⁇ k / (Kk) is satisfied.
  • step S4 the control program force
  • the pressure by the pressurizing mechanism 10 and the atmospheric pressure by the vacuum pump 13 are determined by setting such parameters.
  • step S5 the control program force vacuum pump 13 is activated, and the atmospheric pressure in the transfer space R in the vacuum chamber 11 is reduced to P [Pa] to adjust the atmospheric pressure. .
  • step S6 the control program force pressurizing mechanism 10 is operated to raise the substrate support 15 and thereby transfer the transfer material 2 on the transfer substrate 3 to the transfer material 2. Press copy 4 with pressure M.
  • step S7 the transfer program 4 is pressed and the ultraviolet lamp 7 is operated to irradiate the transfer material 2 with ultraviolet rays to cure the transfer material 2.
  • step S8 the control program force is again activated to actuate the pressurizing mechanism 10 to lower the substrate support 15 so that the transfer mold 4 is peeled from the transfer material 2.
  • a transfer material 17 having a convex pattern 17A having a height of k [nm] corresponding to the concave pattern 4A is formed.
  • step S9 the operation of the control program force vacuum pump 13 is stopped, the atmospheric pressure in the transfer space R in the vacuum chamber 1 is returned to atmospheric pressure, and the transfer substrate 3 on which the formed transfer material 17 is placed. Is taken out from the vacuum chamber 1: L through an opening / closing means (not shown), and the transfer is completed.
  • the control program executes the depth K [nm] of the concave pattern 4A of the transfer mold 4 and the convex pattern 17A of the transfer 17 in the present embodiment.
  • the pressing means 10 pressurizing mechanism
  • the pressure adjusting means 13 vacuum pump
  • the imprint apparatus includes the transfer substrate 3 on which the transfer material 2 is placed, the transfer mold 4 provided with the concave pattern 4A, and the transfer mold 4 having an effective pressure Mo.
  • [Pa] generates a pressing force so that it can be pressed against the transfer material 2 on the transfer substrate 3, and in this example, the pressing mechanism 10 and the transfer space R in which the transfer mold 4 and the transfer substrate 3 exist.
  • Has pressure adjustment means in this example, vacuum pump 13
  • control means control program, etc.
  • the transfer mold 4A is peeled from the transfer material 2 to form a transfer material 17 having a convex pattern 17A having a height k [nm] corresponding to the concave pattern 4A.
  • Device 100 wherein the control means Based on the depth K [nm] of the pattern 4A and the height k [nm] of the convex pattern 17A of the transferred material 17, the pressing means 10 and the pressure adjusting means 13 are controlled.
  • the imprint apparatus is characterized in that the pressure adjusting means 13 is a pressure reducing means 13.
  • the imprint apparatus is characterized in that the control means controls the pressing means 10 and the pressure adjusting means 13 so that Mo / P ⁇ k / (K k) is satisfied. To do.
  • the imprinting method uses the transfer mold 4 provided with the concave pattern 4A having the depth K [nm] in the atmospheric pressure P [Pa]. Is pressed against the transfer material 2 with effective pressure Mo [Pa], and after the transfer material 2 is cured in the pressed state, the height corresponding to the recess pattern 4A is peeled off.
  • the transfer material 2 is pressed against the fluid transfer material 2 placed on the transfer substrate 3 against the fluid transfer material 2, and the transfer material 2 is compressed by the compression force at that time. As a result, the transfer material 2 is in contact with the concave pattern 4A. A transferred product 17 is formed on the corresponding convex pattern 17A.
  • the transfer substrate 3 is lifted by the pressurizing mechanism 10 to the transfer mold 4 on the fixed side, and the downward force is positively pressed.
  • pressurization using only the transfer mold's own weight there are two cases: pressurization using only the transfer mold's own weight; and in addition to this, the pressurization mechanism actively lowers and pressurizes. is there.
  • pressure M [Pa] in the pressure environment of atmosphere P [Pa] (atmospheric pressure 1 X 10 5 [Pa] or a predetermined reduced pressure environment) (in this example, the pressure to transfer mold 4 is uniform and effective pressure Mo is
  • P [Pa] atmospheric pressure 1 X 10 5 [Pa] or a predetermined reduced pressure environment
  • Mo effective pressure
  • the transfer mold 4 is pressed against the transfer material 2 in the same manner, if the transfer material 2 with the height k [nm] enters the recess 4A with the depth K [nm], the remaining height K k [nm] is obtained.
  • the air layer is confined and compressed by the transfer material having the height k. Therefore, for this air layer, under isothermal conditions, Boyle's law,
  • the pressure reducing means 13 reduces the pressure to a pressure lower than necessary as long as the relationship is satisfied. Or pressing force greater than necessary with pressing means 10 There is no need to generate shearing force. As a result, the device 100 can be reduced in size and simplified.
  • the pressing means 10 and the decompression means 13 are:
  • the height of the transfer material 2 occupies k [nm], and the remaining air layer height is K—k. [nm]
  • the depth K of the recess 4A is set to 100%, among which the transfer material 2 has a height k of 90% and an air layer height K-k of 10%. I just need to
  • the depth K of the recess pattern 4A is set to 100%, of which the transfer material 2 has a height k of 99% and an air layer height K—k of Because it only needs to account for 1%,
  • the imprint apparatus 100 includes input means for inputting the depth K [nm] of the concave pattern 4A and the height k [nm] of the convex pattern 17A.
  • the transfer material 2 when a material that cannot be applied with a very high load (sample, etc.) is used as the transfer material 2, the pressure reducing means 13 that can achieve a high degree of vacuum is used so that the above (Equation 1) is satisfied.
  • the pressing means 10 can be simplified. In this way, the apparatus can be made smaller and simpler than the conventional imprint apparatus, and the cost can be reduced. From this point of view, a more specific application example of the imprint apparatus 100 of the present embodiment will be described below.
  • the transfer mold 4 that is movable with respect to the transfer substrate 2 on the fixed side described above is taken as an example, and is partially different from the configuration of FIG.
  • the explanation will be made using two cases: pressurization only by the weight of the mold 4 and pressurization with the pressurization mechanism 10 being positively lowered.
  • the imprint apparatus 100 preferably presses the transfer mold 4 evenly against the transfer material 2.However, due to the structure of the imprint apparatus 100, the transfer mold 4 and the transfer material 2 are diagonally hit or the transfer mold 4 is a transfer material. If there is a large unevenness in the contact surface with 2, there may be a distribution in the pressing pressure. In this case, set the minimum pressing pressure boy in the distribution so that transfer can be performed reliably!
  • the in-plane minimum pressing pressure Mmin [Pa] of the contact surface between the transfer mold and the transfer material is used.
  • the transfer can be performed even in the worst condition, so that the transfer can be surely performed even in the whole apparatus.
  • the in-plane minimum pressing pressure Mmin [Pa] on the contact surface between the transfer mold 4 and the transfer material 2 is used as the effective pressure Mo, and the pressing means
  • the desired convex pattern 17A of the transferred material 17 can be obtained by doubling the depth K of the concave pattern 4A of the transfer mold 4 and setting the transfer ratio to about 50%, not necessarily high transfer rate. Then, according to (Equation 1) above, the necessary conditions for the imprint apparatus 100 are
  • the imprint apparatus 100 can be further simplified by using the technology for increasing the depth K of the concave pattern 4A of the transfer mold 4 with respect to the height k of the convex pattern 17A desired. .
  • FIG. 4 is an explanatory diagram showing the behavior when the transfer margin is allowed in this way.
  • the effective pressure Mo and the atmospheric pressure P are set in the range where the above (Equation 3) holds, and the transfer mold 4 (depth K of the concave pattern 4A) is used.
  • a transfer type including a transfer substrate 3 on which a transfer material 2 having fluidity under predetermined conditions is mounted, and a concave pattern 4A having a depth of K [nm].
  • 4 and pressing means 10 for generating a pressing force so that the transfer mold 4 is pressed against the transfer material 2 on the transfer substrate 3 at an effective pressure Mo [Pa], and the transfer in which the transfer mold 4 and the transfer substrate 3 exist
  • Pressure reducing means 13 for reducing the atmosphere so that the space R is set to pressure P [Pa].
  • the imprint apparatus 100 forms the transfer 17 having the convex pattern 17A corresponding to the concave pattern 4A and having a height k [nm] smaller than the depth K by peeling off the force.
  • the minimum pressing pressure Mmin may be used as the effective pressure Mo.
  • the imprint apparatus 100 in this case uses the in-plane minimum pressing pressure Mmin [Pa] of the contact surface between the transfer mold 4 and the transfer material 2 as the effective pressure Mo, and the pressing means 10 and the decompression means 13 are ,
  • the imprinting method is such that the transfer mold 4 having the concave pattern 4A having the depth K [nm] is transferred to the transfer material 2 having fluidity in the atmospheric pressure P [Pa]. Is pressed with an effective pressure Mo [Pa], and the transfer material 2 is cured in the pressed state, and then the transfer mold 4 is peeled off, whereby a convexity of height k [nm] corresponding to the recess pattern 4A is obtained.
  • the effective pressure Mo the in-plane minimum pressing pressure M min [Pa] of the contact surface between the transfer mold 4 and the transfer material 2 is used.
  • the atmosphere of the transfer space R in the vacuum chamber 1 of the imprint apparatus 100 described above is changed to a suitable gas such as nitrogen or argon by using a substitution means (not shown) connected to the vacuum chamber 1 before starting the transfer. It is also possible to perform replacement in a dry environment (dry environment).
  • the imprint apparatus 100 is characterized by having gas replacement means for setting the atmosphere of the transfer space R as a dry environment.
  • gas replacement means for setting the atmosphere of the transfer space R as a dry environment.
  • the atmosphere in the transfer space R is replaced with, for example, nitrogen or argon to obtain a dry environment, so The possibility of the occurrence of compression condensation can be completely eliminated. As a result, the design accuracy and transfer margin of the imprint apparatus 100 can be improved.
  • thermoplastic resin is used as a transfer material
  • the case where an ultraviolet curable resin or the like having a small temperature change at the time of imprinting is used as an example of the transfer material 2 (particularly effective in this case), but is not limited thereto. That is, a material that does not have fluidity at room temperature (for example, a thermoplastic resin using a thermal imprint resin) may be used.
  • a material that does not have fluidity at room temperature for example, a thermoplastic resin using a thermal imprint resin
  • the relational expressions (formulas (1) to (4)) similar to those described above are obtained by heating the gas sufficiently between them to be isothermal. Can be established.
  • the volume of the enclosed gas changes due to cooling when it is cured while the transfer mold 4 is pressed against the thermoplastic resin, but since the change is in the direction of volume reduction, at least the transfer rate may be degraded. There is no problem even if it is defined by (Formula 1) to (Formula 4).
  • FIG. 5 is a conceptual configuration diagram illustrating an overall schematic structure of an imprint apparatus 200 according to the present modification, which is another embodiment, and corresponds to FIG. 1 of the embodiment. Parts equivalent to those in FIG. 1 are denoted by the same reference numerals, and description thereof will be omitted or simplified as appropriate.
  • a transfer material 202 made of thermoplastic resin is placed on the transfer substrate 3, and an ultraviolet lamp having a configuration related to ultraviolet irradiation from the configuration of FIG. 7, the optical fiber 6, the ultraviolet irradiation lens 8, and the transparent support window 9 are omitted.
  • the transfer mold 4 is supported by the mold holding mechanism 5 as in FIG. 1.
  • a mold heater 218 is provided above the transfer mold 4, and the substrate support 15 on which the transfer substrate 3 is placed is also provided.
  • a substrate heater 219 is provided.
  • a chamber heater 220 is newly provided in the vacuum chamber 11. The other configuration is the same as that of the imprint apparatus 100 shown in FIG.
  • FIGS. 6 (a) to 6 (f) are explanatory diagrams conceptually showing each procedure of the imprint method of the present embodiment performed using the imprint apparatus 200 having the above-described configuration. It is a figure corresponding to.
  • a transfer material 202 thermoplastic resin
  • nozzle 16 not shown in FIG. 5
  • a solution or reaction-curing resin is applied to form a layer of the transfer material 202 (FIG. 6 (b)).
  • the substrate heater 219 is operated to elevate the temperature of the transfer material 202 to evaporate the solvent, or to cause the reaction-curing type resin to undergo a thermal reaction so that the fluidity at room temperature disappears (see FIG. 6 (c)).
  • the vacuum pump 13 is operated to reduce the atmospheric pressure of the transfer space R in the vacuum chamber 11 to P [Pa].
  • the mold heater 218 and the chamber heater 220 are operated to raise the temperature of the transfer material 202 until the glass transition temperature is reached or higher (FIG. 6 (d)). .
  • the pressurizing mechanism 10 is operated to raise the substrate support 15 and thereby transfer the transfer mold 4 to the transfer material 202 on the transfer substrate 3. Press with pressure M.
  • the substrate heater 219, the mold heater 218, and the chamber heater 220 are stopped and cooled while the transfer mold 4 is pressed, and the transfer material 202 is cured (FIG. 6 (e)).
  • the pressurizing mechanism 10 is operated again to lower the substrate support 15 and thereby the transfer mold 4 is peeled off from the transfer material 202, thereby corresponding to the concave pattern 4A.
  • the transferred material 217 having the convex pattern 217A having the height k [nm] is formed (FIG. 6 (f)).
  • the operation of the vacuum pump 13 is stopped, the atmospheric pressure of the transfer space scale in the vacuum chamber 11 is returned to atmospheric pressure, and an opening / closing means (not shown) for the transfer substrate 3 on which the formed transfer material 217 is placed is provided. Through the vacuum chamber 11 to complete the transfer.
  • the pressurizing mechanism 10 and the vacuum pump 13 are not limited to the depth K of the concave pattern 4A of the transfer mold 4 and the height k of the convex pattern 217A of the transfer material 202.
  • the effective pressure Mo when the transfer mold 4 is pressed and the pressure P in the transfer space R the pressing force is generated and the pressure is reduced so that the deviations of (Equation 1) to (Equation 4) are satisfied.
  • FIG. 7 shows each hand of the imprint method performed using the imprint apparatus 200 configured as described above. It is a flowchart which shows order conceptually. The contents of this flowchart show the work performed by the control means in the imprint apparatus 200, and mainly represent, for example, a flow from the viewpoint of a control program. In this flowchart, for example, a thermal method (heating method) is adopted.
  • a thermal method heating method
  • step S1 the transfer mold 4 is set.
  • step S2 the control program instructs the transfer substrate 3 to be set.
  • a layer of a transfer material 202 (thermoplastic resin) is formed on the transfer substrate 3 by using an apparatus prepared separately in advance. If the transfer material 202 has not been formed in advance, then in step S2, the control program force the nozzle 16 (not shown in FIG. 5) provided in the vacuum chamber 11 on the transfer substrate 3 in an appropriate manner.
  • a liquid transfer material 202 thermoplastic resin solution or reaction-curing resin
  • the solvent is evaporated by elevating the temperature, or the reaction-curing resin is thermally reacted to cure it to such an extent that fluidity at normal temperature is lost.
  • step S3 parameters are set. Specifically, the depth K of the concave pattern 4A and the height k of the convex pattern 7A formed on the transfer material 202 are input.
  • the pressurizing mechanism 10 and the vacuum pump 13 are pressed by the depth K of the concave pattern 4 A of the transfer mold 4, the height k of the convex pattern 7 of the transfer material 202, and the transfer mold 4 is pressed.
  • the pressure Mo when applied and the pressure P in the transfer space R the pressing force is generated and the pressure is reduced so that any of the above (Formula 1) to (Formula 4) is satisfied. .
  • step S4 the control program force
  • the pressure by the pressurizing mechanism 10 and the atmospheric pressure by the vacuum pump 13 are determined by setting such parameters.
  • step S5 the control program force vacuum pump 13 is operated to reduce the atmospheric pressure of the transfer space R in the vacuum chamber 1 to P [Pa].
  • step S5a in addition to the control program power substrate heater 219, the mold heater 218 and the chamber heater 220 are operated, and the transfer material 202, transfer substrate until the transfer material 202 reaches the glass transition temperature or higher.
  • step S6 the control program force pressurizing mechanism 10 is operated to provide a substrate support. 15 is raised, and the transfer mold 4 is pressed against the transfer material 202 on the transfer substrate 3 with a pressure M.
  • step S7 the substrate heater 219, the mold heater 218, and the chamber heater 220 are stopped and cooled while the transfer mold 4 is pressed, and the transfer material 202 is cured.
  • step S8 the control program force is again activated to actuate the pressurizing mechanism 10 to lower the substrate support 15 so that the transfer mold 4 is removed from the transfer material 202.
  • a transfer product 217 having a convex pattern 217A having a height of k [nm] corresponding to the concave pattern 4A is formed.
  • step S9 the operation of the control program force vacuum pump 13 is stopped, the atmospheric pressure in the transfer space R in the vacuum chamber 11 is returned to atmospheric pressure, and the transfer substrate on which the formed transfer material 217 is placed is placed. 3 is removed from the vacuum chamber 11 through an opening / closing means (not shown) to complete the transfer.
  • the control program executes the depth K [nm] of the concave pattern 4A of the transfer mold 4 and the convex portion of the transferred material 217. Based on the height k [nm] of the pattern 217A, the pressing means 10 (pressure mechanism) and the pressure adjusting means 13 (vacuum pump) are controlled.
  • the imprint apparatus 100 in each of the above embodiments is a transfer type including a transfer substrate 3 on which a transfer material 2 having fluidity under predetermined conditions is placed, and a concave pattern 4A having a depth of K [nm]. 4 and a pressure mechanism 10 that generates a pressing force so that the transfer mold 4 is pressed against the transfer material 2 on the transfer substrate 3 at an effective pressure Mo [Pa], and the transfer mold 4 and the transfer substrate 3 exist.
  • a vacuum pump 13 that depressurizes the atmosphere so that the space R has a pressure P [Pa].
  • the transfer die 4 is transferred to the transfer material 4 2 is an imprint apparatus 100 that forms a transfer 17 having a convex pattern 17A having a height of k [nm] corresponding to the concave pattern 4A by peeling off from the press pattern 10.
  • the pressurizing mechanism 10 and the vacuum pump 13 are: Generate pressing force and reduce pressure so that MoZP ⁇ kZ (K—k).
  • the transfer mold 4 provided with the concave pattern 4 ⁇ having the depth K [nm] in the atmospheric pressure P [Pa] is transferred to the transfer material 2 having fluidity.
  • pressing with effective pressure Mo [Pa] curing the transfer material 2 in the pressed state, and then peeling off the transfer mold 4 makes the convex pattern of height k [nm] corresponding to the concave pattern 4A.
  • 17 is an imprint method for forming a transfer material 17 having A, and pressing and setting of atmospheric pressure are performed so that MoZP ⁇ kZ (K ⁇ k).
  • an imprint transfer mold is manufactured using an electron beam, and a patterned magnetic recording medium is manufactured as an example of a magnetic recording medium using the imprint transfer mold.
  • FIGS. 8 (a) to 8 (f) are cross-sectional views showing an example of a process for manufacturing an imprint transfer mold according to this application example, and FIG. 9 is based on FIGS. 8 (a) to 8 (f).
  • FIG. 5 is a process diagram showing details of a method for producing an imprint transfer mold. First, as shown in FIGS. 8 (a) and 9, after polishing and cleaning a substrate 71 having a material force such as Si wafer or glass, an electron beam resist for electron beam is applied on the substrate 71 by spin coating or the like. A film 72 is formed. Next, the electron beam resist film 72 is pre-beta, and as shown in FIG.
  • the electron beam resist film 72 is exposed with an electron beam to form a latent image 72a (“signal recording” in FIG. 9). ).
  • the electron beam resist film 72 is developed to form a groove 72b as shown in FIG. 8C, and then the electron beam resist film 72 is post-beta.
  • a nickel alloy thin film 73 is formed on the surface of the electron beam resist film 72 and the substrate 71 by sputtering, vapor deposition, or electroless plating.
  • the substrate 71 is etched using the electron beam resist film 72 as a mask instead of directly forming the nickel alloy film 73 on the surface of the electron beam resist film 72, and the groove 72b is copied to the substrate 71.
  • the line resist film 72 may be removed, and the nickel alloy film 73 may be formed on the surface of the substrate 71 on which the groove corresponding to the groove 72b is formed.
  • the nickel layer 74 is formed by applying nickel electrolysis to the surface of the nickel alloy thin film 73 using the nickel alloy thin film 73 as an electrode. Then, as shown in FIG. 8 (f), after the nickel layer 74 is peeled from the substrate 71, a master stamper 74A is obtained by polishing the upper surface of the nickel layer 74 in FIG. 8 (f). Instead of the -packet layer 74, a nickel alloy layer may be formed by electroplating, and the peeled nickel alloy layer may be used as a stamper.
  • a sub-master stamper whose shape is inverted is obtained by attaching nickel again to the master stamper 74A by electric power.
  • a baby stamper with the same shape as the master stamper can be obtained by applying nickel to the submaster stamp. Further, a new stamper may be produced by transferring the shape of the baby stamper.
  • the imprint transfer mold and the imprint transfer product according to the present application have a density of 500 Gb psi (Gbit / inch 2 ) or more, particularly an ultrafine pattern corresponding to a very high surface recording density of about 1 to 10 Tbpsi. Is effective. Specifically, by using a pattern transfer mold having a pit interval of about 25 nm, it becomes possible to produce a high-density pattern recording medium having a transfer force recording density of about lTbpsi. [0105] In order to realize this, an electron beam lithography apparatus capable of forming a high-definition pattern is used for the manufacturing method of the mask 12 having the concavo-convex portion in the transfer mold manufacturing method of the above application example. It is desirable.
  • the electron beam lithography apparatus includes a substrate coated with a resist, a mechanism for moving the substrate in the horizontal direction, and a rotary stage for rotating the substrate.
  • the resist is irradiated with an electron beam exposure beam. It is an X- ⁇ type electron beam drawing device for drawing.
  • a dot pattern is formed by drawing at a constant interval while simultaneously rotating in the radial direction while rotating the stage. At that time, it is possible to provide a dot row in a spiral shape without deflecting the electron beam during rotation.
  • the resist It is also possible to draw concentric dot rows by exposing the light beam by changing the deflection amount of the electron beam in a sawtooth shape so as to draw concentric circles.
  • a region provided with a servo pattern for address extraction and track position control may be produced.
  • a patterned magnetic recording medium 80 called a patterned medium as a hard disk or patterned hard disk can be divided into a servo pattern portion 81 and a patterned data track portion 82 as shown in FIG.
  • the dot pattern of the data track portion 82 is shown only on the outer peripheral portion and the inner peripheral portion, but it is the default and omitted, and actually it covers the entire effective radius of the disk. Exist. Further, there is a servo pattern portion 81 other than that shown in FIG.
  • the swing arm head 83 is configured to be swingable in the radial direction of the magnetic recording medium 80, and reads or writes data recorded in the magnetic recording area of the magnetic recording medium 80.
  • the servo pattern 81 has a rectangular pattern indicating address information and track detection information, and a line extending in the radial direction across the track from which clock timing is extracted. A pattern or the like is formed.
  • the servo pattern unit 81 has a form similar to that of the current hard disk recording medium, but adopts a servo pattern of a new format optimized for the turned-on medium, and uses the current hard disk medium. Different pattern shapes and forms may be used.
  • This patterned magnetic recording medium 80 is produced by forming a latent image that has been drawn and exposed by the pattern drawing method described above, and directly etching the recording material using a resist mask formed by development. Power S that can be done, mass production efficiency will be extremely low. Therefore, it is desirable to use a manufacturing method using an imprint method as a mass production process. This involves etching a recording material, etc., using a resist pattern that has been mass-transferred by producing a transfer mold for imprinting from a resist mask and performing transfer using the imprint transfer mold. This is a method for manufacturing a patterned magnetic recording medium.
  • FIG. 11 is a process diagram showing an example of manufacturing a patterned magnetic recording medium
  • FIGS. 12 (a) to 12 (e) and FIGS. 13 (f) to 13 (m) are processes of manufacturing a patterned magnetic recording medium. It is a sectional view showing details. The process for producing the patterned magnetic recording medium described below is merely an example.
  • the process of producing a patterned magnetic recording medium is roughly divided into a transfer product forming process, an imprint process, an etching process, a nonmagnetic material filling process, and a protective film (lubricating film) forming process capability. Thus, these steps are sequentially performed.
  • a substrate serving as a base for a magnetic recording medium made of special carotenite tempered glass, Si wafer, aluminum plate, or other material. Prepare 116.
  • the recording film layer 101 is formed on the substrate 116 by sputtering or the like.
  • a laminated structure as indicated by a broken line in FIG. 12 (b) such as a soft magnetic underlayer, an intermediate layer, and a ferromagnetic recording layer.
  • a metal mask layer 102 such as Ta or Ti is formed on the recording film layer 101 by sputtering or the like. Then, the transfer substrate 3 is produced. On this metal mask layer 102, for example, polymethyl methacrylate resin (PMMA) t and a thermoplastic resin resin resist are formed as a transfer material 202 by spin coating or the like.
  • PMMA polymethyl methacrylate resin
  • thermoplastic resin resin resist are formed as a transfer material 202 by spin coating or the like.
  • the transfer mold 4 is set in the imprint apparatus 200 shown in FIG. 5 so that the uneven surface faces the transfer material 202 as shown in FIG. 12 (c). That is, the transfer mold 4 is supported by a mold holding mechanism 5 (not shown in FIG. 12 (c)) and set on a mold holding member 218, while the transfer substrate 3 on which the transfer material 202 is placed is a substrate support 1 Hold on 5.
  • the vacuum pump 13 is driven as necessary to depressurize the working chamber 11, and then a transfer material as necessary.
  • a transfer material as necessary.
  • press For example, since the glass transition point of polymethyl methacrylate resin (PMMA) is around 100 ° C, it has fluidity when heated to 120-200 ° C (for example, about 160 ° C) above the glass transition temperature.
  • pressing 1 ⁇ Press with a pressing force of LOOOOkPa (eg about lOOOkPa).
  • LOOOOkPa eg about lOOOkPa
  • the vacuum in the working chamber 1 is several hundred Pa or less (for example, 10 Pa). It is desirable to make a vacuum state.
  • the thickness of the concavo-convex pattern of the transfer mold 4 is set to a thickness that accommodates bubbles generated when the transfer mold 4 is pressed. That is, the thickness of the concavo-convex pattern formed on the surface of the transfer mold 4 is set to be thicker than the thickness of the concavo-convex portion of the transfer material 202 that is finally left on the surface of the transfer material 217.
  • the transfer material 202 is used as an etching mask and a metal mask using CHF gas or the like.
  • Etch layer 102 Etch layer 102.
  • the remaining transfer material 202 is removed from the wet process or O gas.
  • the recording film layer 101 is etched by dry etching using Ar gas or the like with the metal mask layer 102 as an etching mask. Further, as shown in FIG. 13 (j), the remaining metal mask layer 102 is removed by either wet process force dry etching.
  • the surface of the nonmagnetic material 104 is polished and flattened by etch back, chemical polishing, or the like.
  • a structure in which the recording material is separated by the non-recording material 104 can be manufactured.
  • the protective film (lubricating film) forming step as shown in FIG. 13 (m), for example, the protective film 105 and the lubricating film 106 of the recording film layer 101 are formed on the surface by a coating method or a dating method.
  • the pattern recording medium is completed.
  • a patterned magnetic recording medium can be manufactured through the above steps.
  • the imprint process of the present embodiment the process using the thermal imprint apparatus 200 in each of the above embodiments will be described as an example. However, the UV imprint apparatus 100 and the like will be described. Even if the imprint process is performed using the embodiment, the patterned magnetic recording medium can be similarly produced.
  • FIG. 1 is a conceptual configuration diagram showing an overall schematic structure of an imprint apparatus according to an embodiment of the present invention.
  • FIG. 2 is an explanatory diagram conceptually showing each procedure of an imprint method performed using the imprint apparatus of FIG. 1.
  • FIG. 3 is a flowchart conceptually showing each control procedure of the imprint method performed using the imprint apparatus of FIG. 1.
  • FIG. 4 is an explanatory diagram showing the behavior when a transfer margin is allowed.
  • FIG. 5 Overall schematic structure of a modified imprint apparatus using thermoplastic resin as a transfer material. It is a conceptual block diagram showing construction.
  • FIG. 6 is an explanatory diagram conceptually showing each procedure of an imprint method performed using the imprint apparatus of FIG.
  • FIG. 7 is a flowchart conceptually showing each control procedure of the imprint method performed using the imprint apparatus of FIG.
  • FIG. 9 is a process diagram showing details of the method for producing an imprint transfer mold.
  • FIG. 10 is a plan view showing a patterned magnetic recording medium manufactured using a transfer mold.
  • FIG. 11 is a process diagram showing an example of producing a patterned magnetic recording medium.
  • FIG. 12 is a cross-sectional view showing details of a process for producing a patterned magnetic recording medium.

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Abstract

Lorsqu'un poinçon (4) de motif concave (4A) est en contact par pressage avec un matériau de transfert (2) d'une certaine fluidité, le matériau de transfert (2) est durci puis le poinçon (4) est arraché, ceci produisant ainsi un objet transféré (17) de motif convexe (17A) correspondant au motif concave (4A). Un mécanisme de mise sous pression (10) et une pompe à vide (13) sont réglés pour satisfaire à la relation Mo/P ≥ k/(K - k), où K est la profondeur du motif concave (4A) du poinçon (4), k est la hauteur du motif convexe (17A) du matériau de transfert (2), Mo est une pression efficace lorsque le poinçon (4) est comprimé, et P est une pression à l'intérieur de l'espace de transfert R. Ainsi, même lorsque de l'air passe et se trouve scellé dans le motif concave (4A) du poinçon (4), le transfert peut être réalisé sans problème.
PCT/JP2007/052115 2006-02-14 2007-02-07 dispositif d'impression et procédé d'impressioN WO2007094213A1 (fr)

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JP2020525322A (ja) * 2017-06-29 2020-08-27 ユニヴェルシテ デクス−マルセイユUniversite D’Aix−Marseille マイクロトランスファー成形方法及びそれから得ることができるパターン基板
JP7229184B2 (ja) 2017-06-29 2023-02-27 ユニヴェルシテ デクス-マルセイユ マイクロトランスファー成形方法及びそれから得ることができるパターン基板
US11472097B2 (en) 2018-05-31 2022-10-18 Canon Kabushiki Kaisha Imprint apparatus, imprint method, and article manufacturing method
CN109728054A (zh) * 2019-01-02 2019-05-07 京东方科技集团股份有限公司 显示面板及其制备方法、显示装置
CN110262186A (zh) * 2019-06-25 2019-09-20 京东方科技集团股份有限公司 一种纳米压印模具、纳米压印装置和纳米压印方法
CN110262186B (zh) * 2019-06-25 2021-12-03 京东方科技集团股份有限公司 一种纳米压印模具、纳米压印装置和纳米压印方法
CN115338954A (zh) * 2022-09-19 2022-11-15 福建航融建材科技有限公司 一种混凝土空心砌块生产成型加工设备及成型加工方法
CN115338954B (zh) * 2022-09-19 2024-02-06 福建航融建材科技有限公司 一种混凝土空心砌块生产成型加工设备及成型加工方法

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